CN102549064A

CN102549064A - Crosslinked polyolefin polymer blends

Info

Publication number: CN102549064A
Application number: CN2010800431178A
Authority: CN
Inventors: S·雅格布; A·D·韦斯特伍德; J·R·休伯
Original assignee: Exxon Chemical Patents Inc
Current assignee: ExxonMobil Chemical Patents Inc
Priority date: 2009-10-02
Filing date: 2010-09-24
Publication date: 2012-07-04
Anticipated expiration: 2030-09-24
Also published as: EP2483351A1; WO2011041230A1; SG178395A1; CN102549064B; US20120077898A1; US8742019B2; EP2483351B1; KR20120061944A; US9040601B2; KR101450408B1; US8765834B2; US20120202915A1; US20120309862A1

Abstract

Crosslinked polyolefin blends, methods for their production, and articles made of the same are provided. In at least one specific embodiment, the polyolefin blends comprise a first polymer formed in a first reactor and a second polymer formed in a second reactor. The first and second polymers, as well as the resulting blend, may comprise units derived from propylene, ethylene, and a diene. The blended composition can then be compounded with one or more coagents, antioxidants, and/or other additives and crosslinked, preferably by exposure to energetic photons. The crosslinked polymers are particularly useful for making fibers, films, and nonwovens.

Description

The cross-linked polyolefin blend polymer

The cross reference of related application

The right of priority of the U.S. Provisional Patent Application that the application requires to submit on October 2nd, 2009 number 61/248,190, the disclosure of the document is introduced this paper as a reference in full.The application is involved in the Patent Application No. of submitting on May 30th, 2,008 12/130,745, and the document is incorporated herein for reference in full.

Background technology

Polyolefin polymer and blend polymer are well-known because of their versatility and applicabilitys in wide variety of applications.Especially, many polyolefin polymers (comprising the for example multipolymer of ethene of propylene and other terminal olefin) are suitable for requiring the application of good tensility, elasticity and intensity very much.Have excellent tension property and elastic material and except making durable goods, also be used for making various disposable products, include but not limited to incontinence pad, disposable diaper, training pants, clothes, underwear, tSportswear, automobile decoration (automotive trim), weather strip, packing ring and furniture upholstery.For clothes, tensility and elasticity are to allow material to provide precision to comply with the attribute of performance of cooperation for wearer's health.

Though known many materials at room temperature show excellent stress-strain behavior and elasticity, often hope that the elongation and between systole or in summer in automotive interior provide of resilient material during reusing, under the temperature that raises or reduce comply with or cooperation reliably.Elasticity at elevated temperatures is important to during whole temperature cycle, keeping tight tolerance also.Specifically, the resilient material that is used for repeated wear property clothes or clothing must be kept their integrity and elasticity after washing.

Spandex (a kind of block polyurethane urea resilient material) is current to be used for various durable fabrics.For example, but washing clothes, fabric have been used for, durable and disposable furniture, bedding etc. by the fiber that Spandex processes.Be similar to conventional uncrosslinkedly based on polyolefinic resilient material, the goods of being processed by Spandex are possible loss integrity, shape and elasticity when the temperature of experience rising.Therefore, Spandex is not suitable for adopting high temperature fiber, and for example many knitting (co-knitting) altogether of trevira use.

The polymkeric substance based on propylene with favorable elasticity is known and has been used for the clothes that can stretch.For example, referring to U.S. Patent number 6,525,157 with U.S. Patent number 6,342,565.Specifically, U.S.6,342,565 disclose the softness that comprises polyolefinic blend, anti-permanentset (set-resistant), annealed fiber.This blend has and is less than or equal to 12, and the modulus in flexure of 000psi also comprises 75-98wt% first polymeric constituent and 2-25wt% second polymeric constituent.First polymeric constituent is to have a 80wt% propylene and 20wt% ethene at least at the most, 25-70 ℃ pass through fusing point (Tm) that DSC measures and less than the propylene-ethylene polymkeric substance of the melting heat of 25J/g.Second polymeric constituent is to have through what DSC recorded greater than 130 ℃ fusing point with greater than the upright structure of the melting heat of 120J/g the rule isotactic polyprophlene to be arranged.This fiber is presented at and is equal to or less than 80% anti-permanentset property under 400% tensile deformation.This polyolefin blends it is said uncrosslinked basically.

U.S. Patent number 6; 500; 563 disclose two kinds of dissimilar polyacrylic blends, comprise by having less than the Vestolen PP 7052 of 110 ℃ Tm and the sequence with propylene derived that isotaxy arranges and the blend processed less than the propylene-ethylene copolymers of 105 ℃ Tm.

U.S. Patent Application Publication 2006/0183861 discloses crosslinked elastic composition, comprises by the blend made from at least a component that is selected from multiple functionalized propenoate, multiple functionalized methacrylic ester, functionalized poly butadiene resin, functionalized cyanurate and allyl group isocyanuric acid ester and at least a polymkeric substance based on propylene that is selected from the component blend of hindered phenol, phosphorous acid ester and hindered amine.This blend is through being exposed in the electron beam irradiation and crosslinked.

Being described among EP946640, EP964641, EP969043 and the EP1098934 of isotactic polyprophlene, shock resistance improvement amount based on the rubber of ethylene-propylene or low density ethylene copolymer with as elastomeric three blend of components based on propylene of expanding material.

WO 04/014988 has described the for example blend of poly-alpha-olefin of isotactic polyprophlene and non-functionalized softening agent.WO 03/040233 also discloses and has contained isotactic polyprophlene serves as impact modifier as main matrix phase with based on the multipolymer of propylene two-pack blend.

EP1003814 and U.S.6,642,316 disclose the elastomeric two-pack blend based on ethene of a spot of isotactic polyprophlene and main amount.EP0374695 discloses visually two-pack blend uniformly, yet uses 40wt% or the multipolymer based on propylene still less.WO00/69963 has described the film of being processed by the two-pack blend, and this two-pack blend contains 75-98wt% and has the elastomerics based on propylene-ethylene less than the melting heat of 25J/g.

Other relevant reference comprises US publication 2006/102149; 2005/0107529; 2005/0107530; 2005/0131142 and 2005/0107534.

Many polyolefin blends for example in the prior art those disclosed for example form pellet from the intermediate storage purpose before fiber, film, non-woven fabric, extruding coating and the moulded product being shaped as goods.Yet the known pellet stability that in the period that prolongs, shows difference of some in these compsns causes the agglomeration of pellet and causes the coming down in torrents property and the flowable of the difference of pellet.

Therefore still need novel and improved material based on propylene, they show good pellet stability, also show good tensility and the elasticity that is used for wide variety of applications simultaneously.

Summary of the invention

The present invention relates to by two kinds that in two or more reactor drums, produce or the blend polymer of more kinds of polymer formation and the method for manufacture of this kind blend polymer.In some embodiments, said blend polymer is through being exposed in the high-energy photon and crosslinked at least in part, and can further be configured as goods, especially comprises fiber, film and non-woven fabric etc.Blend polymer described herein shows improved mechanical property and elasticity and improved pellet stability when comparing with analog material as known in the art.

The accompanying drawing summary

Fig. 1 has described the stress (MPa) with elongation (%) variation of uncrosslinked material of the present invention and contrast material.

Fig. 2 has described the stress (MPa) with elongation (%) variation of crosslinked material of the present invention and contrast material.

Fig. 3 has described to contain and the stress (MPa) with elongation (%) variation that does not contain the material of auxiliary agent and contrast uncrosslinked material.

Detailed Description Of The Invention

The present invention relates to polyolefin polymer blend and preparation method thereof.More particularly, embodiment of the present invention be included in form in first reactor drum first based on the polymkeric substance of propylene and second the blend that in second reactor drum, produces based on the polymkeric substance of propylene.Can these blend polymers and various additional component be comprised auxiliary agent, inhibitor, elastomer-assisted, Vestolen PP 7052, additive, filler and the compounding of additive wet goods.Can make it further crosslinked at least in part through letting said blend be exposed in the high-energy photon from the source that comprises ultraviolet (UV) line, x-ray and gamma-radiation.In some embodiments, the crosslinked of blend polymer reaches via electron beam irradiation.Blend polymer described herein shows improved pellet stability when comparing with the similar blend that in single reactor drum, prepares, and has outstanding mechanical property and elasticity.Especially; When with blend polymer described herein and auxiliary agent, inhibitor or the two compounding and when crosslinked subsequently, they when with the same manner preparation and have and have improved performance for example peak stress, peak value elongation and tensile deformation when similar composition does not still have the cross-linked polymer blend of auxiliary agent and inhibitor to compare.To more describe said blend polymer and preparation method thereof in detail below.

Constitute the polymkeric substance of blend

The present invention is included in first polymkeric substance for preparing in first reactor drum and second polymkeric substance that in second reactor drum, prepares.Said first polymkeric substance and said second polymkeric substance normally based on the polymkeric substance of alkene, in some embodiments, are based on the homopolymer or the multipolymer of propylene separately.Term as used herein " multipolymer " is meant that this comonomer type comprises the comonomer derived from terminal olefin and diene through the materials with at least two kinds of different comonomer type copolymerization preparations.One or more other different comonomer type also can be included in the multipolymer at this, so that this multipolymer definition multipolymer of comprising terpolymer and comprising four kinds or more kinds of different copolymer monomer types.Term as used herein " monomer " or " comonomer " can be meant the monomer that is used for forming polymkeric substance; The unreacted chemical cpd that promptly is polymerization form before; And can be meant the monomer (this paper is also referred to as " unit of monomer derived ") after it has been attached in the polymkeric substance, because polyreaction has than its still less Wasserstoffatoms before polyreaction usually.This paper has discussed different monomers, comprises propylene monomer, vinyl monomer and diene monomers.

In some embodiments of the present invention, each multipolymer of propylene and one or more comonomers naturally of first polymkeric substance and second polymkeric substance.Comonomer can be a straight or branched.In one or more embodiments, the straight chain comonomer can comprise ethene or C ₄-C ₈Terminal olefin includes but not limited to 1-butylene, 1-hexene and 1-octene.The side chain comonomer can comprise 4-methyl-1-pentene, 3-Methyl-1-pentene and 3,5,5-trimethylammonium-1-hexene.In one or more embodiments, comonomer can comprise vinylbenzene.

In some embodiments, each multipolymer of propylene and ethene (also also can comprise other comonomer) naturally of first polymkeric substance and second polymkeric substance.For example, said first polymkeric substance and said second polymkeric substance can be identical or different, and unit that can the about 99wt% derived from propylene of each self-contained about 75-and the about about 25wt% units derived from ethylene of 1-.In some embodiments, first polymkeric substance can comprise the unit of the about 20wt% ethylene derivative of about 12-, or the unit of about about 18wt% ethylene derivative of 14-.In identical or other embodiment, second polymkeric substance can comprise the unit of the about 10wt% ethylene derivative of about 3-or the unit of about about 8wt% ethylene derivative of 5-.In one embodiment of the invention, first polymkeric substance has the ethylene content bigger than second polymkeric substance.For example, first polymkeric substance can comprise 3wt% at least than second polymkeric substance more, or 5wt% at least, or 7wt% at least, or the unit of 9wt% ethylene derivative at least.

In one or more embodiments here, second polymkeric substance also can comprise the ethene of less amount, or does not comprise ethene, so that second polymkeric substance can be HOPP or polyacrylic random copolymers (RcP).Exemplary RCP comprises the about 8wt% comonomer of about 1-usually, or about about 5wt% comonomer of 2-.In one or more embodiments, the RCP comonomer is an ethene.

Randomly, first polymkeric substance and second polymkeric substance can also comprise one or more diene.Term " diene " is defined as the hydrocarbon compound with two unsaturated sites, promptly has the compound of two two keys that connect carbon atom.Depend on context, term " diene " broadly refers to the diene monomers before polymerization in this patent, for example, form the part of polymerisation medium, or the diene monomers after polymerization begins (being also referred to as diene monomers unit or diene deutero-unit).Being suitable for exemplary diene of the present invention comprises; But be not limited to; Divinyl, pentadiene, hexadiene (for example 1; The 4-hexadiene), heptadiene (for example 1,6-heptadiene), octadiene (for example 1,7-octadiene), nonadiene (for example 1; The 8-nonadiene), decadiene (for example 1; The 9-decadiene), 11 carbon diene (for example 1,10-11 carbon diene), 12 carbon diene (for example 1,11-12 carbon diene), oleatridecadiene (for example 1; The 12-oleatridecadiene), 14 carbon diene (for example 1,13-14 carbon diene), 15 carbon diene, 16 carbon diene, 17 carbon diene, 18 carbon diene, 19 carbon diene, 20 carbon diene, 21 carbon diene, 22 carbon diene, two oleatridecadienes, tetracosa carbon diene, 25 carbon diene, 26 carbon diene, heptacosadiene, 28 carbon diene, 29 carbon diene, 30 carbon diene and have the polyhutadiene of molecular weight (Mw) less than 1000g/mol.The instance of straight chain acyclic dienes includes, but are not limited to 1,4-hexadiene and 1,6-octadiene.The instance of side chain acyclic dienes includes, but are not limited to the 5-methyl isophthalic acid, 4-hexadiene, 3,7-dimethyl--1,6-octadiene and 3,7-dimethyl--1,7-octadiene.The instance of the alicyclic diene of monocycle includes, but are not limited to 1,1, and 5-cyclooctadiene and 1,7-encircle 12 carbon diene.The instance that many rings are alicyclic to condense with the bridging cyclic diolefine includes, but are not limited to tetrahydroindene; Norbornadiene; The methyl tetrahydroindene; NSC 7352; Dicyclo (2.2.1) heptan-2, the 5-diene; And thiazolinyl-, alkylidene-, cycloalkenyl group-and the ring alkylidene norbornylene [comprising, for example 5-methylene-2-norbornene, 5-ethidine-2-norbornylene, 5-propenyl-2-norbornylene, 5-isopropylidene-2-norbornylene, 5-(4-cyclopentenyl)-2-norbornylene, 5-cyclohexylidene base-2-norbornylene and 5-vinyl-2-norbornylene].The instance of the substituted alkene of cycloalkenyl group includes, but are not limited to VCH, allyl group tetrahydrobenzene, vinyl cyclooctene, 4 vinyl cyclohexene, allyl group cyclodecene, ethene basic ring dodecylene and Fourth Ring 12 carbon diene.In some embodiments of the present invention, diene is selected from 5-ethidine-2-norbornylene (ENB); 1, the 4-hexadiene; 5-methylene-2-norbornene (MNB); 1, the 6-octadiene; The 5-methyl isophthalic acid, the 4-hexadiene; 3,7-dimethyl--1,6-octadiene; 1; 1; Vinyl norbornene (VNB); Dicyclopentadiene (DCPD) (DCPD) and their combination.In one or more embodiments, diene is ENB.

Said first polymkeric substance and said second polymkeric substance can comprise the diene deutero-unit of identical or different amount.In some embodiments, said first polymkeric substance and the about 6wt% diene of each self-contained 0.05-of said second polymkeric substance deutero-unit.In other embodiments, said first polymkeric substance comprises the about 5.0wt% diene of about 0.5-deutero-unit, or the about about 3.0wt% diene of 1.0-deutero-unit.In identical or different embodiment, second polymkeric substance comprises the about 1.0wt% diene of about 0.1-deutero-unit.

Said first polymkeric substance and said second polymkeric substance can have 5,000,000g/mol or lower weight-average molecular weight (Mw), about 3; 000,000g/mol or lower number-average molecular weight (Mn), about 10; 000,000g/mo l or lower z average molecular weight (Mz) and 0.95 or the bigger g ' index that uses isotactic polyprophlene to measure with the weight-average molecular weight (Mw) of polymkeric substance as benchmark; They can pass through size exclusion chromatography, and for example 3D SEC is also referred to as GPC-3D and measures.

In one or more embodiments, said first polymkeric substance and said second polymkeric substance have identical or different Mw, and have approximately 5 separately, and 000-about 5,000; The Mw of 000g/mol, or about 10, and 000-about 1,000; 000 Mw, or about 20, the Mw of 000-about 500,000; Or about 50, the Mw of 000-about 400,000, wherein Mw mensuration as described herein.

In one or more embodiments, said first polymkeric substance and said second polymkeric substance can have identical or different Mn, and can have approximately 2 separately, and 500-about 2; 500, the Mn of 000g/mol, or about 5,000-about 500; 000 Mn, or about 10, the Mn of 000-about 250,000 or about 25; The Mn of 000-about 200,000, wherein Mn such mensuration as described herein.

In one or more embodiments, said first polymkeric substance and said second polymkeric substance have identical or different Mz, and have approximately 10 separately, and 000-about 7,000; The Mz of 000g/mol, or about 50, and 000-about 1,000; 000 Mz, or about 80, the Mz of 000-about 700,000; Or about 100, the Mz of 000-about 500,000, wherein Mz such mensuration as described herein.

The MWD of said first polymkeric substance and said second polymkeric substance (MWD=(Mw/Mn)), being sometimes referred to as " heterogeneity index " (PDI) can be identical or different, and can be about 1.5-40.In some embodiments, said MWD can have 40 or 20 or 10 or 5 or 4.5 the upper limit and 1.5 or 1.8 or 2.0 lower limit.In one or more embodiments, said first polymkeric substance or second polymkeric substance or both MWD are about 1.8-5.The technology of determining molecular weight (Mn, Mw and Mz) and MWD (MWD) can be referring to U.S. Patent number 4,540,753 (Cozewith; Ju and Verstrate) and (its be incorporated herein supply the U.S. put into practice purpose with reference to) and the reference wherein quoted, Macromolecules, 1988; 21 volumes; 3360 pages people such as () Verstrate (its be incorporated herein supply the U.S. put into practice purpose with reference to) and the reference wherein quoted and according to U.S. Patent number 6,525; The capable disclosed program of 157 the 5th hurdle 1-44, this patent are incorporated herein for reference in view of the above in full.

In one or more embodiments; Said first polymkeric substance and said second polymkeric substance can have 0.95 or bigger; Or at least 0.97, or g ' index value of at least 0.99, wherein g ' the limiting viscosity that is to use isotactic polyprophlene is measured with the Mw of this polymkeric substance as benchmark.For use in this article, g ' index definition is:

η wherein _bBe the limiting viscosity of polymkeric substance, η ₁Be the limiting viscosity that has the straight-chain polymer of same viscosity-average molecular weight (Mv) with this polymkeric substance, η ₁=KM _v ^α, K and α be straight-chain polymer observed value and should with the identical instrument that is used for g ' index measurement on obtain.

In one or more embodiments, said first polymkeric substance and said second polymkeric substance can have identical or different density, and this density is at room temperature measured according to ASTM D-1505 TP, can be about 0.85g/cm ³-about 0.92g/cm ³, or about 0.87g/cm ³-0.90g/cm ³, or about 0.88g/cm ³-about 0.89g/cm ³

In one or more embodiments; Said first polymkeric substance and said second polymkeric substance can have the melt flow rate(MFR) that is equal to or greater than 0.2g/10min (MFR, 230 ℃ of 2.16kg weight

) according to ASTM D-1238 (A) test method measuring.The MFR of said first polymkeric substance and said second polymkeric substance can be identical or different.In some embodiments; Said first polymkeric substance or second polymkeric substance or both MFR (230 ℃ of 2.16kg ) are the about 200g/10min of about 0.5g/10min-, or about about 100g/10min of 1g/10min-.In some embodiments; Said first and/or second polymkeric substance has the about 200g/10min of about 0.5g/10min-; Or about about 30g/10min of 2g/10min-; Or about about 30g/10min of 5g/10min-, or about about 30g/10min of 10g/10min-, or the approximately about 25g/10min of 10g/10min-or the approximately MFR of the about 10g/10min of 2g/10min-.

Said first and/or second polymkeric substance can have according to ASTM D1646 measure less than 100; Or less than 75; Or less than 60, or less than 125 ℃ of 30 mooney viscosity ML (1+4) .The mooney viscosity of said first polymkeric substance and said second polymkeric substance can be identical or different.

In one or more embodiments; Said first polymkeric substance or second polymkeric substance or both can have according to the DSC program determination of describing after a while more than or equal to about 0.5 joule/gram (J/g); Be less than or equal to about 80J/g; Or be less than or equal to about 75J/g, or be less than or equal to about 70J/g, or be less than or equal to about 60J/g or be less than or equal to the melting heat (Hf) of about 50J/g.Said first polymkeric substance or second polymkeric substance or the two can also have more than or equal to about 1J/g or more than or equal to the about melting heat of 5J/g.In another embodiment, said first polymkeric substance or second polymkeric substance or the two can have the about 75J/g of about 0.5J/g-, or about about 75J/g of 1J/g-, or the melting heat (Hf) of about about 35J/g of 3J/g-.In some embodiments; Polymkeric substance and compsn can characterize according to their fusing point (Tm) and melting heat; Said performance possibly influenced by the existence of comonomer or space irregularity, and this comonomer or space irregularity hinder the formation of crystallite through polymer chain.In one or more embodiments; Said first polymkeric substance or second polymkeric substance or the two melting heat have the following 30J/g of being limited to or 35J/g or 40J/g or 50J/g or 60J/g or the 70J/g of 1.0J/g or 1.5J/g or 3.0J/g or 4.0J/g or 6.0J/g or 7.0J/g, or the upper limit of 75J/g or 80J/g.The melting heat of said first polymkeric substance and said second polymkeric substance can be identical or different.

Said first polymkeric substance and said second crystallinity of polymer also can be according to percentage (the being % percent crystallinity) expressions of percent crystallinity.In one or more embodiments; Said first polymkeric substance and second polymkeric substance have identical or different percent crystallinity; And one of said polymkeric substance or both % percent crystallinity can be 0.5%-40%; Or 1%-30%, or 5%-25%, wherein % percent crystallinity is according to following DSC program determination.From reference purpose, polyacrylic high-order heat energy is estimated as 189J/g (that is, 100% percent crystallinity equals 209J/g).

Except this crystallinity level, said first polymkeric substance and said second polymkeric substance can have single wide melting transition.Yet polymkeric substance can show the secondary melting peak adjacent with main peak, and still for the purpose of this paper, this type of secondary melting peak together is considered to single fusing point, and wherein the fusing point of this polymkeric substance is thought at the climax of these peaks (with respect to baseline described herein).

Said first polymkeric substance and said second polymkeric substance can have identical or different fusing point, and in some embodiments, one of said first polymkeric substance and said second polymkeric substance or both have and are equal to or less than 110 ℃; Or less than 100 ℃, or less than 90 ℃, or be less than or equal to 80; Or be less than or equal to 75 ℃; Or about 25 ℃-about 80 ℃, or about 25 ℃-about 75 ℃, or about 30 ℃-about 65 ℃ fusing point (through dsc measurement).In these or other embodiment, the fusing point of said second polymkeric substance is greater than the fusing point of said first polymkeric substance, and can be greater than about 105 ℃, or greater than about 110 ℃, or greater than about 115 ℃.

Dsc (DSC) program can be used to measure the melting heat and the melt temperature of said first polymkeric substance and said second polymkeric substance, and the melting heat and the melt temperature of the blend of said first polymkeric substance and said second polymkeric substance.This method is following: weigh up about 0.5 gram polymkeric substance and under about 140 ℃-150 ℃, use " DSC mould " and Myl ar to be pressed into the thickness of about 15-20 mil (approximately 381-508 micron) as liner plate.(do not remove Mylar) in the air and allow this pressed pad to be cooled to envrionment temperature through being suspended on.(23-25 ℃) about 8 days of this pressed pad of annealing at room temperature.When this stage finishes, use punch die to take out about 15-20mg disk and put into 10 mul alumina sample disc from this pressed pad.This sample is put into differential scanning calorimeter (Perkin Elmer Pyris 1 Thermal Analysis System) and is cooled to approximately-100 ℃.Heat this sample to reach about 165 ℃ outlet temperature with 10 ℃/min.Heat output (being recorded as the area under the sample melted peak) is measuring of melting heat and can representes and automatically calculate through Perkin Elmer System with the joule/gram polymkeric substance.Fusing point is recorded as in the fusion range of sample the maximum endothermic temperature with respect to the baseline measures of the temperature variant increase capacity hot in nature of polymkeric substance.

Said first and/or second polymkeric substance can further have 75% or bigger, 80% or bigger, and 82% or bigger, 85% or bigger or 90% or bigger passing through ¹³The triad tacticity of three propylene units that C NMR measures.In some embodiments; Said first polymkeric substance, second polymkeric substance or both triad tacticities are that about 50-is about 99%, or approximately 60-is about 99%, or about 75-about 99%; Or approximately 80-is about 99%, or about 60-about 97%.The triad tacticity discloses the method for describing in 2004/0236042 through U.S. Patent application and measures, and it is for reference that the document is introduced this paper.

The preparation of blend polymer

The particle of being described the polymkeric substance manufacturing of type by this paper is soft when touching generally and possibly is clamminess.Though these performances hope that for many end-use applications possibly there is storage in polymkeric substance and handles problems.For example, the polymer beads of being made by these polymkeric substance (so-called pellet in the industry) has agglomerant tendency (or showing limited flowing), especially at ambient temperature after secular freight house stores.

The agglomeration that has been found that these pellets is caused in the processing of pellet preparation back during initial several hours or several days in distortion between the shelf lives and pellet by polymeric aggregate.Especially, after preparation, polymeric aggregate generally has such shape, promptly this shape be spherical, cylindrical, plate-like or wherein the outside surface of pellet be curved other shape relative with flat surface.Generally speaking, polymeric aggregate is free-pouring, because the curved surface of said pellet has minimum surface in contact and therefore freely slips over each other.Yet, have been found that in some cases, curved pellet surface maybe be between the shelf lives owing to pellet is exerted pressure each other and is flattened, in the time of particularly in being stored in container with remarkable vertical dimension.When polymeric aggregate surface this flattens when taking place, contact area increases significantly, reduces the ability that the pellet surface slips over each other, and causes agglomeration or limited flow of particle in subsequent process steps.

Through improving crystallization rate; The flattening of pellet surface unlikely taken place and pellet can be put hardening in step (finishing step) process in order and free-pouring pellet is provided in conventional polymer, even still like this after storing over a long time under the high envrionment temperature at pellet.

Anti-its flattening property of surface of pellet is relevant with the level of crystallization of polymkeric substance and can measure through the hardness of measurement polymeric aggregate.Generally speaking, measure, in one embodiment, at least 50 Xiao Er A hardness (ASTM 2240) provides the pellet of the agglomeration tendency with reduction.In another embodiment, at least 55 Xiao Er A hardness provides the pellet of the agglomeration tendency with reduction.In another embodiment, at least 60 Xiao Er A hardness provides the pellet of the agglomeration tendency with reduction.Though the pellet by many low crystallinity polymers manufacturings can reach this firmness level after preparation; But spending several days time possibly just reaches this firmness level; Because pellet is along with time crystallization lentamente, especially for wherein kinetics of crystallization is known to polymkeric substance and slower polymkeric substance and the multipolymer based on propylene of multipolymer based on ethene.Method described herein is quickened to make the hardness that pellet can unrestricted flow (even behind long pot life) providing in short-term after the preparation crystallization rate of polymeric aggregate.

In some embodiment of method described herein and blend, with first polymkeric substance and second polymer blending with the preparation blend polymer, this blend polymer when being processed into pellet form with compare by the pellet of the first independent polymer manufacture than short duration (; In back 40 minutes of the initial cooling of pellet; Or in 30 minutes, or in 20 minutes, or in 15 minutes) realize being enough to provide at least 50; Or at least 52; Or at least 55, or at least 57, or the crystalline state of at least 60 Xiao Er A hardness.

Concerning present disclosure, above-mentioned first polymkeric substance generally can be thought low crystallinity polymers, and above-mentioned second polymkeric substance generally can be thought high-crystallinity copolymer.Having been found that can be through reducing said low crystallinity polymers and at least a unitary high-crystallinity copolymer blend that comprises the propylene derived with high-crystallinity or eliminating by the agglomeration tendency of the pellet of low crystallinity polymers manufacturing.Concerning present disclosure, the unitary high-crystallinity copolymer that comprises propylene derived is meant and comprises at least the unit of 90wt% propylene derived and the polymkeric substance with melt temperature of at least 100 ℃.

In some embodiment of method described herein and blend, via the solution blending of the method for preparing polymkeric substance at independent serial or parallel connection polymerization stage with first low crystallinity polymers and second high-crystallinity copolymer.For example, first low crystallinity polymers can prepare in first reactor drum.The ejecta (solution that contains first polymkeric substance) of first reactor drum is transferred to second reactor drum; Wherein necessary catalyzer of contact preparation second high-crystallinity copolymer and monomer, so that in second reactor drum and in the presence of first polymkeric substance, prepare the solution of second polymkeric substance.This is called the tandem reactor method.

Can in solution polymerization reactor, prepare first polymkeric substance and second polymkeric substance.The solution of the polymeric constituent that will be produced by these methods combines to provide first polymkeric substance and the intimate blending of second polymkeric substance between the polymerization period of second multipolymer.Discharge the polymkeric substance of blend and use conventional processing units and technology to be processed into polymer beads, fiber, film, non-woven fabric or other finished product from second reactor drum then.

Perhaps, can be parallel to second high-crystallinity copolymer for preparing in second reactor drum and in first reactor drum, prepare first low crystallinity polymers.In parallelly connected polymerization method, preparation first polymkeric substance and second polymkeric substance in parallel reactor, and the ejecta (solution that contains the phase emergencing copolymer) of each reactor drum is guided to the said ejecta of blend and prepares the equipment of the solution of polymer blend component.Reclaim the polymkeric substance of blend and be processed into polymer beads, fiber, film, non-woven fabric or other finished product from said solution then according to common process equipment and technology.

The series connection that is suitable for preparing blend polymer described herein with and the more detailed description of linked method (comprising use therein polymerizing condition and the catalyzer that is fit to) referring to U. S. application publication number 2004/0024146 and U. S. application publication number 2006/0183861, it is for reference that these two pieces of documents are introduced this paper in full with it.

In alternative embodiment of the present invention, can in the high-pressure solution method, prepare first polymkeric substance and second polymkeric substance.These methods (comprising use therein polymerizing condition and the catalyzer that is fit to) are described in greater detail in the U. S. application publication number 2009/0163642, and the document is introduced this paper as a reference in full.

In some embodiments of the present invention; Be prepared as follows blend polymer of the present invention: in first reactor drum, make the polymers soln polymerization that comprises first polymkeric substance; In second reactor drum, make the polymers soln polymerization that comprises second polymkeric substance; Said first polymers soln is combined with second polymers soln with preparation blend polymer solution, and process said blend polymer solution with the preparation blend polymer.

The performance of blend polymer

In certain embodiments of the invention; Blend polymer through above-mentioned double-reactor method preparation can comprise the about 98wt% of about 45wt%-by pure form, or about about 98wt% of 50wt%-, or about about 98wt% of 60wt%-; Or said first polymkeric substance of about about 98wt% of 70wt%-and about about 55wt% of 2wt%-; Or about about 50wt% of 2wt%-, or about about 40wt% of 2wt%-, or said second polymkeric substance of about about 30wt% of 2wt%-.In another embodiment, with pure form, blend polymer described herein comprises said first polymkeric substance of the about 95wt% of about 80wt%-and said second polymkeric substance of about about 20wt% of 5wt%-.In other embodiments, with pure form, blend polymer described herein comprises said first polymkeric substance of the about 95wt% of about 90wt%-and said second polymkeric substance of about about 10wt% of 5wt%-.

In other embodiments of the present invention, blend polymer can comprise the about 18wt% of about 10-, or total ethylene content of about about 16wt% ethene of 12-.In identical or other embodiment, said blend can comprise the about 5.0wt% diene of about 0.1-deutero-unit, or the about about 3.0wt% diene of 0.5-deutero-unit, or the about about 2.0wt% diene of 1.0-deutero-unit.

In some embodiments; Blend polymer described herein can have the melt flow rate(MFR) according to ASTM D-1238 (A) test method measuring (MFR, 230 ℃ of 2.16kg weight

) of the about 10g/10min of about 1-.In other embodiments, the MFR of said blend is the about 7g/10min of about 3-.

In some embodiments, it is about 10 that blend polymer can have, and 000-is about 200,000g/mo1, or about 20, and 000-is about 150,000, or about 30, the Mn of 000-about 100,000.In identical or other embodiment, it is about 100 that blend polymer can have, and 000-is about 400,000g/mol, or about 150, and 000-is about 300,000, or about 200, the Mw of 000-about 250,000.It is about 10 that blend polymer can also have about 1.5-, or the about MWD of 2.0-about 4.0.In addition, it is about 0.99 that blend polymer can have about 0.94-, or the about g ' of 0.95-about 0.98.

In some embodiments, blend polymer described herein can have greater than about 100 ℃, or greater than about 110 ℃, or greater than about 115 ℃ fusing point.In addition, the melting heat of blend polymer can be less than about 30J/g, or less than about 25J/g, or less than about 20J/g.In some embodiments of the present invention; About greatly at least 5 ℃ of the fusing point of the blend polymer of physical blending rather than the reactor blending preparation of the fusing point that the blend polymer that in above-mentioned double-reactor, prepares has than having that same general is formed but through first polymkeric substance and second polymkeric substance, or about greatly at least 10 ℃.

The compounding of blend polymer

In some embodiments of the present invention, blend polymer described herein can with one or more additional component compoundings.Be suitable for being well known to those skilled in the art and can including, but not limited to auxiliary agent, inhibitor, elastomer-assisted, Vestolen PP 7052, additive, filler and additiveoil with the additional component of blend polymer compounding.In other embodiments, with blend polymer and at least a or multiple auxiliary agent or one or more inhibitors (containing or do not contain other additional component) compounding.In certain embodiments, blend polymer and auxiliary agent and inhibitor compounding.

In one or more embodiments; Each material and component, blend polymer for example described herein can form the compounding blend through the melt-mixing blend with optional one or more auxiliary agents, inhibitor, elastomer-assisted, Vestolen PP 7052, additive, filler and/or additiveoil.Can produce the instance that is used for desired shearing of compounding and blended mechanical means and comprise having kneader or hybrid element and the one or more forcing machine of end or screw thread, forcing machine, common or derotation forcing machine transition, Banbury mixing machine, Farrell continuous mixer and Buss kneaders of mixing with one or more screw rods.Desired blended type and intensity, temperature and the residence time can be through one of above-mentioned machine selection (＜3000RPM) selection reaches together with kneading or hybrid element, screw design and screw speed.

In one or more embodiments, auxiliary agent, inhibitor and/or other additive can be introduced after them in downstream or only with other polymeric constituent simultaneously or under the situation of using forcing machine or Buss kneader after a while.In other embodiments, auxiliary agent, inhibitor and/or other additive can be attached in the polymer product through online compounding, wherein in second polymer formation, said additive are introduced second reactor drum.This eliminates the needs to additional compounding step and equipment.Except said auxiliary agent and inhibitor; Other additive can comprise; But be not limited to anti, static inhibitor, UV stabilizer, pigment, tinting material, nucleator, fire retardant, softening agent, sulfuration or solidifying agent, sulfuration or curing catalyst, tackifier, FLOW IMPROVERS, lubricant, releasing agent, whipping agent, toughener and processing aid.Additive can or add in the blend in masterbatch by pure form.The filler that is suitable for compounding blend polymer of the present invention be know in this area and can comprise granular, fibrous and pulverulent filler.Can be suitable for specific filler of the present invention comprises natural and synthesis of clay, carbon black and zeyssatite etc.

Can will set forth more in detail below with the exemplary composition of blend polymer compounding, but it or not closure that those skilled in the art will approve following description, and can adopt any material that is suitable for blend polymer compounding described herein.

Auxiliary agent

Blend polymer described herein can randomly comprise one or more auxiliary agents.The auxiliary agent that is fit to can comprise liquid and the multiple functionalized propenoate of metal (salt) and methacrylic ester (salt), functionalized poly butadiene resin, functionalized cyanurate and allyl group isocyanuric acid ester.More particularly; The auxiliary agent that is fit to can comprise; But for example be not limited to multiple functionalized vinyl or allylic cpd; Triallylcyanurate, cyanacrylate, tetramethylolmethane tetramethyl-propenoate, ethylene glycol dimethacrylate, diallyl maleate, toxilic acid diine propyl ester, dipropargyl monoene propyl group cyanurate, Diisopropyl azodicarboxylate and analogue and their combination.In one or more embodiments, the auxiliary agent that is fit to comprises triacrylate, and in a specific embodiment, auxiliary agent is a trimethylolpropane trimethacrylate.Commercially available auxiliary agent can be from for example, and Sartomer buys.Exemplary auxiliary agent is Sartomer350.

In one or more embodiments, blend polymer contains 0.1wt% auxiliary agent at least, based on the gross weight of blend.In one or more embodiments, the amount of auxiliary agent (one or more) can be for about about 15wt% of 0.1wt%-, based on the gross weight of blend.In one or more embodiments, the amount of auxiliary agent (one or more) can be about 0.1wt%, and the lower limit of 1.5wt% or 2.0wt% is to about 4.0wt%, and the upper limit of 7.0wt% or 15wt% is based on the gross weight of blend.In other embodiments, the amount of auxiliary agent (one or more) is about 3wt%, based on the gross weight of blend.

Inhibitor

Blend polymer described herein can randomly comprise one or more inhibitors.The instance of inhibitor includes but not limited to quinoline (quinolein), for example trimethylammonium hydroxyquinoline (TMQ); Imidazoles, for example sulfydryl toluyl zinc imidazolate (zincmercapto toluyl imidazole) is (ZMTI); With the inhibitor of routine, hindered phenol for example, lactone, SULPHOSUCCINIC ACID ESTER and hindered amine.Other inhibitor that is fit to can be from for example, and Ciba Geigy Corp. is purchased with trade name Irgafos168, Irganox1010, Irganox3790, IrganoxB225, Irganox1035, Irgafos126, Irgastab410 and Chimassorb944.In one or more embodiments, inhibitor comprises phosphorous acid ester, especially three-(2,4-two-tert-butyl-phenyl) phosphorous acid esters.One or more inhibitors can add in the blend polymer with prevent be shaped or manufacturing operation during degraded and/or Quality Initiative palliating degradation degree better.

In one or more embodiments, blend polymer contains 0.1wt% inhibitor at least, based on the gross weight of blend.In one or more embodiments, the amount of inhibitor (one or more) can be for about about 5wt% of 0.1wt%-, based on the gross weight of blend.In other embodiments, the amount of inhibitor (one or more) can be about 0.1wt%, and the lower limit of 0.15wt% or 0.2wt% is to about 1wt%, and the upper limit of 2.5wt% or 5wt% is based on the gross weight of blend.In other embodiments, the amount of inhibitor (one or more) is about 0.2wt%, based on the gross weight of blend.

Elastomer-assisted

Blend polymer of the present invention can randomly comprise one or more elastomer-assisted components.In at least one particular, the elastomer-assisted component can be or comprise one or more ethylene-propylene copolymers (EP).Preferably, ethylene-propylene polymkeric substance (EP) is amorphous, atactic or unbodied for example, but in certain embodiments, EP can be crystalline (comprising " hemicrystalline ").The percent crystallinity preferred source of EP is from ethene, and whether the percent crystallinity that many disclosed methods, program and technology can obtain to be used to estimate specific material stems from ethene.Can as follows the percent crystallinity of EP be distinguished with the crystallinity of polymer based on propylene: from compsn, remove EP, measure residual crystallinity of polymer then based on propylene.This kind percent crystallinity that the poly percent crystallinity calibration of common use records and this kind percent crystallinity that records are associated with co-monomer content.Percentage percent crystallinity is measured as the percentage of Vilaterm percent crystallinity in the case and therefore confirms to be derived from the source of the percent crystallinity of ethene.

In one or more embodiments, EP can comprise the polyenoid that one or more are optional, especially comprises diene; Therefore, EP can be ethylene-propylene-diene terpolymer (so-called " EPDM ").Optional polyenoid thinks to have any hydrocarbon structure of at least two unsaturated link(age)s, and wherein at least one of unsaturated link(age) easily is incorporated in the polymkeric substance.Second key can partly be participated in polymerization to form long chain branches, still preferably provides at least some to be suitable for after polymerization, solidifying or the sulfurized unsaturated link(age) in the technology subsequently.The instance of EP or EPDM multipolymer comprises those that can trade(brand)name Vistalon obtain from ExxonMobil Chemicals.Some commercial EPDM can obtain with trade name Nordel IP and MG from DOW.The additiveoil of blend in advance before some rubber components (for example, EPDM, for example Vistalon 3666) is included in rubber components combined with thermoplastic material.The type of employed additiveoil will be the type of uniting use usually with specific rubber components.

Optional polyenoid instance comprises; But be not limited to; Divinyl, pentadiene, hexadiene (for example 1; The 4-hexadiene), heptadiene (for example 1,6-heptadiene), octadiene (for example 1,7-octadiene), nonadiene (for example 1; The 8-nonadiene), decadiene (for example 1; The 9-decadiene), 11 carbon diene (for example 1,10-11 carbon diene), 12 carbon diene (for example 1,11-12 carbon diene), oleatridecadiene (for example 1; The 12-oleatridecadiene), 14 carbon diene (for example 1,13-14 carbon diene), 15 carbon diene, 16 carbon diene, 17 carbon diene, 18 carbon diene, 19 carbon diene, 20 carbon diene, 21 carbon diene, 22 carbon diene, two oleatridecadienes, tetracosa carbon diene, 25 carbon diene, 26 carbon diene, heptacosadiene, 28 carbon diene, 29 carbon diene, 30 carbon diene and have the polyhutadiene of molecular weight (Mw) less than 1000g/mol.The instance of straight chain acyclic dienes includes, but are not limited to 1,4-hexadiene and 1,6-octadiene.The instance of side chain acyclic dienes includes, but are not limited to the 5-methyl isophthalic acid, 4-hexadiene, 3,7-dimethyl--1,6-octadiene and 3,7-dimethyl--1,7-octadiene.The instance of the alicyclic diene of monocycle includes, but are not limited to 1,1, and 5-cyclooctadiene and 1,7-encircle 12 carbon diene.The instance that many rings are alicyclic to condense with the bridging cyclic diolefine includes, but are not limited to tetrahydroindene; Norbornadiene; The methyl tetrahydroindene; NSC 7352; Dicyclo (2.2.1) heptan-2, the 5-diene; And thiazolinyl-, alkylidene-, cycloalkenyl group-and ring alkylidene norbornylene [comprise, for example 5-methylene-2-norbornene, 5-ethidine-2-norbornylene, 5-propenyl-2-norbornylene, 5-isopropylidene-2-norbornylene, 5-(4-cyclopentenyl)-2-norbornylene; 5-cyclohexylidene base-2-norbornylene and 5-vinyl-2-norbornylene].The instance of the substituted alkene of cycloalkenyl group includes, but are not limited to VCH; The allyl group tetrahydrobenzene; The vinyl cyclooctene; 4 vinyl cyclohexene; The allyl group cyclodecene; Ethene basic ring dodecylene and Fourth Ring 12 carbon diene.

In another embodiment; The elastomer-assisted component can comprise; But be not limited to styrene/butadiene rubbers (SBR), styrene/isoprene rubber (SIR), styrene/isoprene/butadiene rubber (SIBR), styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-ethylene/butylene-styrene block copolymer (SEBS), hydrogenated styrene-ethylene block copolymer (SEB), SIS (SIS), styrene-isoprene block copolymer (SI), hydrogenated styrene-isoprene block copolymer (SEP), hydrogenated styrene-isoprene-styrene block copolymer (SEPS), styrene-ethylene/butylene-ethylene block copolymer (SEBE), styrene ethylene styrene block copolymer (SES), ethylene-vinyl/butylene block-copolymer (EEB), ethylene-vinyl/butylene/styrene block copolymer (hydrogenation BR-SBR segmented copolymer), ethylene-vinyl/butylene-ethylene block copolymer (EEBE), ethylene-vinyl/'alpha '-olefin block copolymers, polyisoprene rubber, polybutadiene rubber, isoprene divinyl rubber (IBR), polysulphide, paracril, propylene oxide polymer, star-branched butyl rubber and halogenated star-branched butyl rubber, brominated butyl rubber, Chlorobutyl, star-branched polyisobutene rubber, star-branching bromination butyl (polyisobutene/isoprene copolymer) rubber; Gather (iso-butylene-copolymerization-ring-alkylated styrenes); Preferred iso-butylene/methylstyrene copolymer is an iso-butylene/brooethyl vinylbenzene, iso-butylene/brooethyl vinylbenzene, iso-butylene/1-chloro-4-methyl-benzene, halogenated isobutylene cyclopentadiene for example, and iso-butylene/1-chloro-4-methyl-benzene and their mixture.Preferred elastomer-assisted component comprises hydrogenated styrene-ethylene/butylene-styrene block copolymer (SEBS) and hydrogenated styrene-isoprene-styrene block copolymer (SEPS).

The elastomer-assisted component can also be or comprise tree elastomer.At rubber technology (RUBBER TECHNOLOGY), the 179-208 page or leaf is described in (1995) tree elastomer by Subramaniam.The tree elastomer that is fit to can be Malaysia's (Malaysian) rubber, SMRCV for example, and SMR5, SMR10, SMR20 and SMR50 and their mixture, wherein this tree elastomer has 30-120, more preferably 100 of 40-65 ℃ of mooney viscosities (ML 1+4).Carry out at this mooney viscosity experimental evidence ASTM D-1646 that relates to.

The elastomer-assisted component can also be or comprise one or more viton.A kind of suitable commercially available viton comprises NATSYN ^TM(Goodyear Chemical Company) and BUDENE ^TM1207 or BR1207 (Goodyear Chemical Company).The rubber of hoping is high-cis-polyhutadiene (cis-BR).So-called " cis-polyhutadiene " or " high-cis-polyhutadiene " are meant and use 1, the 4-cis-polybutadiene, and wherein the amount of cis component is at least 95%.An instance of high-cis polybutadiene commerical prod is BUDENE ^TM1207.

The elastomer-assisted component can be pressed 50phr at the most in one embodiment, in another embodiment, presses 40phr at the most, in another embodiment, by the amount existence of 30phr at the most.In one or more embodiments, the amount of auxiliary rubber component can from about 1,7 or the lower limit of 20phr to about 25,35 or the upper limit of 50phr.

Vestolen PP 7052

In one or more embodiments, compounding blend polymer described herein can contain the Vestolen PP 7052 of additional content.Term as used herein " Vestolen PP 7052 " is meant any polymkeric substance of being thought " Vestolen PP 7052 " (as reflection at least one patent or the publication) by those skilled in the art and homopolymerization, anti-impact and the unregulated polymer that comprises propylene widely.Preferably, the Vestolen PP 7052 that uses in the compsn described herein has the fusing point greater than 110 ℃, comprises 90wt% propylene units at least, and contains those unitary isotactic sequences.Vestolen PP 7052 can also comprise atactic sequence or syndiotactic sequence, or both.Vestolen PP 7052 can also comprise that syndyotactic basically sequence so that polyacrylic fusing point are greater than 110 ℃.Vestolen PP 7052 is derived from propylene monomer (that is, only having propylene units) or main derived from propylene (more than 80% propylene) only, and rest part is derived from alkene, especially ethene, and/or C ₄-C ₁₀Terminal olefin.As point out in other place of this paper, some Vestolen PP 7052 have high MFR (for example 10 15 or the lower limit to 25 of 20g/10min to the upper limit of 30g/10min).Other Vestolen PP 7052 has lower MFR, for example has " classification " Vestolen PP 7052 less than 1.0 MFR.With high MFR those possibly be preferred for easy processing or compounding.

Additiveoil

Blend polymer described herein can also randomly comprise one or more additiveoils.Term " additiveoil " comprise " treated oil " and " extending oil " both.For example, " additiveoil " can comprise hydrocarbon ils and softening agent, for example organic ester and synthetic softening agent.Many additiveoils stem from petroleum fractions, and have specific ASTM title, and this depends on whether they belong to alkane, cycloalkanes or aromatic hydrocarbon oil classification.Other type of additiveoil comprises MO, alpha-alefinically synthetic oil; For example liquid polybutylenes is for example with trade mark

product sold.Can also use except that based on the additiveoil the oil of oil, for example be derived from the oil of coal tar and Stockholm tar, and synthetic oil, for example polyolefine material (SpectraSyn for example ^TMAnd Elevast ^TM, all by ExxonMobil Chemical Company supply).

Those of ordinary skill will recognize use which type oil with the specific combined thing, can confirm the suitable amounts (quantity) of oil to be added in addition.The additiveoil approximately amount of about 300 weight parts of 5-/100 weight part blends exists.

In some embodiments, additiveoil comprises polybutylenes oil.Preferred polybutylenes oil has the Mn less than 15,000, and comprises and contain 3-8 carbon atom, more preferably the unitary homopolymer of alkene deutero-or the multipolymer of 4-6 carbon atom.In one or more embodiments, polybutylenes is the homopolymer or the multipolymer of C4 raffinate.Be called " polybutylenes " polymkeric substance preferred low-molecular weight polymer the embodiment example for example; At SYNTHETIC LUBRICANTS AND HIGH-PERFORMANCE FUNCTIONAL FLUIDS 357-392 (Leslie R.Rudnick&Ronald L.Shubkin; Ed., Marcel Dekker 1999) in state (hereinafter " polybutylenes treated oil " or " polybutylenes ").

In one or more embodiments, the polybutylenes treated oil is to have iso-butylene deutero-unit and optional 1-butylene deutero-unit and/or the unitary multipolymer of 2-butylene deutero-at least.In one embodiment; Polybutylenes is the homopolymer of iso-butylene; Or the multipolymer of iso-butylene and 1-butylene or 2-butylene, or the terpolymer of iso-butylene and 1-butylene and 2-butylene, wherein iso-butylene deutero-unit accounts for the 40-100wt% of multipolymer; 1-butylene deutero-unit accounts for the 0-40wt% of multipolymer, and 2-butylene deutero-unit accounts for the 0-40wt% of multipolymer.In another embodiment, polybutylenes is multipolymer or terpolymer, and wherein iso-butylene deutero-unit accounts for the 40-99wt% of multipolymer, and 1-butylene deutero-unit accounts for the 2-40wt% of multipolymer, and 2-butylene deutero-unit accounts for the 0-30wt% of multipolymer.In another embodiment; Polybutylenes is said three kinds of unitary terpolymers; Wherein iso-butylene deutero-unit is the 40-96wt% of this multipolymer, and 1-butylene deutero-unit is the 2-40wt% of this multipolymer, and 2-butylene deutero-unit is the 2-20wt% of this multipolymer.In another embodiment, polybutylenes is the homopolymer or the multipolymer of iso-butylene and 1-butylene, and wherein iso-butylene deutero-unit is the 65-100wt% of this homopolymer or multipolymer, and 1-butylene deutero-unit is the 0-35wt% of this multipolymer.The commercial embodiments of the treated oil that is fit to comprises PARAPOL ^TMSeries treated oil or derive from Soltex Synthetic Oils and Lubricant s or derive from polybutylenes grade or the Indopol of BP/Innovene ^TMOil.

In certain embodiments, treated oil (one or more) can be by 1-60, or 2-40, or 4-35, or 5-30 weight part/100 weight part blends exist.

Use

Blend polymer of the present invention whether (no matter compounding) can be shaped or be molded into various finished products through adjustment method well-known to those having ordinary skill in the art.These goods can include, but are not limited to film, fiber, non-woven fabric, coating, moulded product etc.Finished product can for example be extruded through any suitable method, blowing, injection moulding, melt and spray, spunbond, compression moulding, fiber sprinning and other method known to those skilled in the art be shaped.But blend of the present invention especially can be used for the application of requirement tensile elasticity material, for example disposable diaper, training cover, incontinence pad, clothes, underwear, tSportswear, automobile decoration, weather strip, packing ring and furniture upholstery etc.

Crosslinked

Blend polymer of the present invention (no matter no matter whether carry out compounding as stated and whether be shaped as finished product) can be crosslinked at least in part through the whole bag of tricks as known in the art.Making the crosslinked a kind of such method of said blend polymer at least in part is that said blend is exposed in the high-energy photon.Especially; The crosslinked of said blend can be realized as follows: said blend is exposed in the electromagnetic radiation of frequency greater than visible frequency for example near ultraviolet radiation, EUV (extreme ultraviolet radiation), soft x-ray (soft x--ray), hard x-ray (hard x-ray), gamma-radiation and high-energy gamma-rays.In certain embodiments of the invention, crosslinked through electron beam irradiation or " e-bundle " radiation realization.

The radiation of E-bundle is the ionization energy form that is characteristic with its low penetration and high dose rate usually.Electronics is to produce through the equipment that is called accelerator, and this accelerator can produce pulse or successive bundle.Term " bundle " is meant and comprises any area that is exposed in the electronics, and this area can be from focus to wideer area, for example line or.Electronics produces through a series of negative electrodes (electrically heated tungsten filament), and this negative electrode produces the electronics of high density.Make these electronics quicken to cross electromotive force then.Usually in keV to MeV scope (wherein eV representes electron-volt), this depends on desired penetration depth to this accelerating potential.Radiation dose also has rad tolerance with Gray (unit) usually, and wherein 1Gy equals 100rad, or more generally, 10kGy equals 1Mrad.Commercial e-bundle unit usually 50keV to greater than 10MeV (million electron volt) energy region in.

In one or more embodiments here, make blend polymer at least in part or the goods that formed by blend polymer are crosslinked or solidify so that they become heat-resisting.Term as used herein " heat-resisting " is meant polymer compsn or the ability of being tested through high temperature thermal deformation described herein by the goods that polymer compsn forms.Term as used herein " curing ", " crosslinked ", " partly solidified at least " with " is partial cross-linked at least " to be meant that compsn has 2wt% insolubles at least based on the gross weight of compsn.In one or more embodiments, compsn described herein can solidify so far forth, promptly makes to use YLENE through the Soxhlet extraction 3wt% at least to be provided as solvent; Or 5wt% at least, or 10wt% at least, or 20wt% at least; Or 35wt% at least, or 45wt% at least, or 65wt% at least; Or 75wt% at least, or 85wt% at least, or be less than the 95wt% insolubles.

In a specific embodiment, crosslinked through polymkeric substance experience e-bundle described herein radiation is realized.The e-beam device that is fit to can be from E-BEAM Services, Inc. or PCT Engineered Systems, and LLC obtains.In a specific embodiment, approximately 100kGy or lower dosage adopt electronics with irradiation repeatedly.The source can be any electron beam device of operating to the scope greater than 10MeV at about 50Kev with the power output that can supply required dosage.Can electronic voltage be adjusted to suitable level, this level can be, for example, 100,000eV; 300,000eV; 1,000,000eV; 2,000,000eV; 3,000,000eV or 6,000,000eV.The equipment that is used for the wide region of radiopolymerization thing and polymer product is obtainable.

Effectively radiation is generally according to the about 100kGy of about 10kGy-, the about 90kGy of preferably approximately 20-, or the about about 80kGy of 30-, or approximately the dosage of the about 60kGy of 50-carries out.of this embodiment specific aspect in, at room temperature carry out radiation.

Do not hope to receive theoretical constraint, it is believed that two kinds of competition processes at the polymkeric substance that comprises propylene and ethene, for example carry out after the radiation of polymkeric substance of the present invention described herein.In the part that contains pending methyl group (for example those polymer units of derived from propylene) of polymer chain, the carbon atom in the main polymer chain is responsive to the chain rupture under radiation, and this causes molecular weight to reduce.Radiative process also makes the carbon of the skeleton that constitutes polymer chain and the bond rupture between the Wasserstoffatoms, thereby produces the radical that can be used for the radical crosslinking of adjacent polymer chains.Therefore, radiation causes crosslinked, and this makes up polymer network, and causes fracture, and this destroys the formation of wide polymer network.To have good stretching and elastic polymkeric substance in order providing, to hope to reduce chain rupture and encourage the crosslinked of adjacent polymer chains simultaneously.

In the polymkeric substance that mainly contains propylene, the dominant mechanism that when radiation, takes place is fracture.On the other hand, in polyethylene polymer, dominant mechanism is crosslinked.Therefore the unit that in rich propylene polymer blends described herein, comprises ethylene derivative improves crosslinked and the minimizing chain rupture, and causes improved crosslinked.In addition, non-conjugated diene is in blend polymer comprising also to the bigger advantage of crosslinked generation in the whole blend polymer among the ENB for example.

In order further to optimize the blend polymer of this paper and to improve crosslinkedly, can before radiation, in the compounding step, auxiliary agent and inhibitor be added in the blend polymer preparation.Do not hope equally to receive theoretical constraint, it is believed that auxiliary agent improves crosslinked behavior, and inhibitor suppresses chain rupture.Therefore, when with do not have auxiliary agent, inhibitor or the two polymer phase than the time, total effect is improved crosslinked.In other words, the length aspect keeps longer to the polymer chain of blend polymer of the present invention described herein owing to the fracture that reduces, thereby in blend polymer, forms the cross-linked network of the bigger distance of continuity.Crosslinked improved tensile deformation, elongation, stress and other mechanical property that causes polymkeric substance again of this raising.

In another embodiment, except the e-beam-curable, can also through be exposed in one or more chemical reagent realize crosslinked.Exemplary chemical reagent includes but not limited to superoxide and other free-radical generating agent, sulphur compound, phenolic resin and silicon hydrate.of this embodiment specific aspect in, linking agent is fluid or is converted to fluid so that it can be administered on the goods equably.The fluid linking agent comprises it being gas (for example sulfur dichloride), liquid (Trigonox C for example; Can obtain from Akzo Nobel), the solution (dicumyl peroxide acetone for example; Or its suspension-s (for example; Suspension-s or the emulsion of dicumyl peroxide in water, or based on the peroxy oxygen reduction system) those compounds.

Exemplary superoxide includes, but are not limited to dicumyl peroxide; Di-t-butyl peroxide; T-butylperoxyl benzoate; Lucidol; Cumene hydroperoxide; Cross the sad tert-butyl ester; Methyl ethyl ketone peroxide; 2,5-dimethyl--2,5-two (t-butyl peroxy) hexane; Peroxo-lauryl and t-butyl peroxy-acetate.When using, peroxide firming agent generally is selected from organo-peroxide.The instance of organo-peroxide includes but not limited to, di-t-butyl peroxide; Dicumyl peroxide; The tert-butyl peroxide cumyl; α, α-two (t-butyl peroxy) diisopropyl benzene; 2,5-dimethyl--2,5-two (t-butyl peroxy) hexane; 1,1-two (t-butyl peroxy)-3,3,5-trimethyl-cyclohexane; Butyl-4, two (t-butyl peroxy) valerates of 4-; Lucidol; Lauroyl peroxide; Dilauroyl peroxide; 2,5-dimethyl--2,5-two (t-butyl peroxy) hexene-3 and their mixture.In addition, can use peroxo-diaryl, ketone peroxide, peroxy dicarbonate, peroxyester, dialkyl, hydroperoxide, peroxy ketal and their mixture.

In one or more embodiments, can use hydrogen silylation (hydrosilylation) technology to carry out crosslinked.

In one or more embodiments, under inertia or limited oxygen atmosphere, carry out crosslinked.The atmosphere that is fit to can provide through utilizing helium, argon gas, nitrogen, carbonic acid gas, xenon and/or vacuum.

Can promote with crosslinking catalyst through chemical reagent or through radiating is crosslinked; For example organic bases, carboxylic acid and organometallic compound comprise the carboxylate salt (for example dibutyl tin laurate, dioctyl tin maleate, dibutyltin diacetate, two sad dibutyl tins, stannous acetate, stannous octoate, lead naphthenate, zinc octoate, cobalt naphthenate etc.) of organic titanate and complex compound or lead, cobalt, iron, nickel, zinc and tin.Accomplish under the radiating situation via uv-radiation, can be employed in the UV radiation and exist one or more UV sensitizing agents that produce radical down to promote crosslinked.This type of UV sensitizing agent is as known in the art; And comprise halogenation multinuclear (polynuclear) ketone; Be selected from the organic carbonyl compound and the carbonylation phenol nuclear SULPHURYL CHLORIDE (carbonylated phenol nuclear sulfonyl chloride) of alkyl phenyl ketone (alkyl phenone), UVNUL MS-40 and three ring fused ring compounds.

The performance of cross-linked polymer blend

Crosslinked at least in part blend described herein provides the optimization that is well suited for various uses material with favorable mechanical performance and elasticity and the combination of improved pellet stability.Especially, blend of the present invention shows than has similar composition but the better pellet stability of the blend that in single reactor drum, prepares.The crosslinked compounding blend that contains at least a auxiliary agent and at least a inhibitor described herein when with the same manner preparation but also show better mechanical property and elasticity when not having the similar cross-linked composition of auxiliary agent and inhibitor to compare.

Further find astoundingly; In crosslinked blends described herein, comprise auxiliary agent and inhibitor and have like top more detailed described synergistic effect, this cause with comprise auxiliary agent or inhibitor but do not have the two similar compsn to compare improved performance.

The method that provides as the present invention and the result of prescription; In one or more embodiments, the melt temperature that blend polymer of the present invention has than having same composition but about at least 5 ℃ of the melt temperature height of the blend polymer of physical blending through said polymkeric substance rather than reactor blending formation.

In identical or other embodiment, the polymer blend composition that comprises auxiliary agent of this paper shows than the same manner preparation and has bigger peak stress and/or the peak value elongation of polymkeric substance that same composition does not still have auxiliary agent.In some embodiments, the polymer blend composition that comprises auxiliary agent of this paper shows than the same manner preparation and has same composition in crosslinked back does not still have the bigger tensile deformation of polymkeric substance of auxiliary agent to improve.

In identical or other embodiment, the polymer blend composition that comprises inhibitor of this paper shows than the same manner preparation and has bigger peak stress and/or the peak value elongation of polymkeric substance that same composition does not still have inhibitor.In some embodiments, the polymer blend composition that comprises inhibitor of this paper shows than the same manner preparation and has same composition in crosslinked back does not still have the bigger tensile deformation of polymkeric substance of inhibitor to improve.

In other embodiments, the polymer blend composition that comprises auxiliary agent and inhibitor of this paper shows than the same manner preparation and has bigger peak stress and/or the peak value elongation of polymkeric substance that same composition does not still have auxiliary agent and/or inhibitor.In some embodiments, the polymer blend composition that comprises auxiliary agent and inhibitor of this paper shows than the same manner preparation and has same composition in crosslinked back does not still have the bigger tensile deformation of polymkeric substance of auxiliary agent and/or inhibitor to improve.

Embodiment

Can further describe above-mentioned argumentation with reference to following non-limiting example.

Use parallel reactor configuration and bicyclic pentadiene metallocene catalyst system preparation five kinds of blend polymers (being expressed as A to E) through above-mentioned double-reactor method.The performance of blend (comprising first polymkeric substance and second polymer properties that constitute blend) is reported in the following table 1.

Table 1

The molecular weight characteristics of blend polymer A to E and thermal property are shown in the following table 2.Also show have similar composition but with the identical characteristics of the comparative polymer of single reactor made.Specifically, comparative polymer is as Vistamaxx from ExxonMobil Chemical Co. ^TM6102 are purchased, MFR that it comprises about 16wt% ethene and has about 2g/10min.

Table 2

Blend ID number	A	B	C	D	E	Contrast
							Mn	98700	90800	96500	55900	22200	110000
Mw	235000	210000	230000	205600	204500	235000
							MWD	2.4	2.3	2.4	3.7	9.2	2.1
g’	0.95	0.96	0.96	0.97	0.98	0.98
							Tm(℃)	114	119	117	119	119	106
Hf(J/g)	3.7	4.8	4.8	4.4	4.5	1.9

Embodiment 1-11

Then with blend polymer A to E and Vestolen PP 7052, auxiliary agent, inhibitor or their combination compounding.Every kind of compsn of preparation in Brabender thermoplastic material compounding machine.The pellet of blend A to E added under 150 ℃ melt temperature among the Brabender that has blanket of nitrogen together with inhibitor kept 3 minutes.Then temperature is reduced to 140 ℃ and add auxiliary agent, inhibitor and/or Vestolen PP 7052 and mixed about 2 minutes and obtain even matter blend.Sheet material that on compression press, the compounding blend is molded as the thickness with 75 mils then and film with thickness of 10 mils.

Use e-bundle radiation (at first with 50kGy, then with 60kGy) to make the compounding preparation (this paper is designated embodiment 1 to 6) of gained crosslinked.The composition of embodiment 1-6, processing condition and mechanical property are reported in the following table 3.

Also through same program, A to E prepares the comparative example by blend polymer, and difference is that blend does not contain auxiliary agent, inhibitor or Vestolen PP 7052.The composition of comparative example 7-11, processing condition and mechanical property are reported in the following table 4.

PP9122 is that the unit and the rest part that contain the 2-3wt% ethylene derivative are polyacrylic polypropylene random copolymer (RCP).PP9122 has MFR (2.16kg, 230 ℃) and the 0.9g/cm of 2.1g/10min ³Density.It is 140kPsi that 1% secant modulus in flexure records through ASTM D790A.PP 9122 can be purchased from ExxonMobil Chemical Company.

Sartomer350 is can be from Sartomer Company, the trimethylolpropane trimethacrylate auxiliary agent that Inc. is purchased.

Irgafos168 is the inhibitor that can be purchased from Ciba Specialty Chemicals.

Solidifying the physicals of estimating compsn before and afterwards.According to ASTM 2240 tested for hardness, and according to the tensile deformations of ASTM D412 at room temperature and 70 ℃ of following test blends.For room temperature and 70 ℃ of tests of tensile deformation, under test temperature on the anchor clamps under 50% tension force aged samples 30 minutes and after anchor clamps take off, at room temperature annealing 30 minutes.Use Soxhlet extractor (extraction time=12 hour) to carry out YLENE Soxhlet solvent extraction test according to ASTMD5492 to solidified sample to understand the level of cross-linked material after the e-beam-curable.The result is expressed as: the weight of percentage YLENE insolubles=after extraction/and in extraction weight * 100 before.

Table 3

Table 4 (comparative example)

Can find out from the contrast of those mechanical propertys of the mechanical property of embodiment 1-6 and comparative example 7-11, in blend polymer of the present invention, add the remarkable improvement that at least a auxiliary agent and at least a inhibitor cause mechanical property.For example; In the peak stress observed value raising that is presented at the embodiment 1-6 that contains auxiliary agent and inhibitor after crosslinked with the contrast of afterwards peak stress difference before the radiation of the e-of all embodiment bundle (promptly; Improve), and the peak stress observed value of comparative example 7-11 reduces (that is, worsening).The similar contrast of 70 ℃ of tensile deformation values of all embodiment shows, though all samples shows the improvement (by the indication that reduces of tensile deformation %) of tensile deformation, the improvement of those samples that contains auxiliary agent and inhibitor is much bigger.

The elasticity that top embodiment further specifies crosslinked blends is improved through adding non-conjugated diene.This is by embodiment 1 and 7 and the contrast of all the other embodiment reflection; This embodiment 1 and 7 is by blend A preparation and comprise very low-level diene (0.19wt%ENB), and these all the other embodiment are by blend B, C, D and the E preparation of diene content from 1.41 to 1.87wt%.For example, embodiment 1 and 70 ℃ of tensile deformations of 7 are keeping substantially the same with the crosslinked back of e-bundle radiating, and the tensile deformation of all the other embodiment is improved after radiation significantly.

Fig. 1 shows by the improved tensile property for preparing the polymer blending deposits yields through the double-reactor method, even crosslinked before still like this.Especially, Fig. 1 shows the uncrosslinked blend of

embodiment

1,3 and 4 and the stress with elongation change of two kinds of comparative polymer blends in single reactor drum, preparing.

Fig. 2 shows the improved tensile property that is produced by the cross-linked polymer blend that in the double-reactor method, forms.Especially, Fig. 2 shows

embodiment

1,3 and 4 and the stress with elongation change of the similar cross-linked polymer blend that in single reactor drum, prepares.

Fig. 3 shows by in blend polymer of the present invention, adding the improved tensile property that auxiliary agent produces.Especially, Fig. 3 shows the embodiment 2 that contains auxiliary agent at crosslinked front and back and the embodiment 8 that the do not contain auxiliary agent stress with elongation change after crosslinked.

For ease, provide various special test programs above and be used to measure some performance for example tensile deformation, elongation at break, Xiao Er A hardness etc.Yet; When those of ordinary skill has been read this patent and hope whether mensuration compsn or polymkeric substance have the specified property that provides in the claim; Then can follow any open or sophisticated method or testing sequence and measure this performance, but the program that provides especially is preferred.Each claim should be interpreted as the result who contains any of these program, even possibly produce the degree of Different Results or observed value to distinct program.Therefore, those skilled in the art should expect the experimental bias that is reflected in the performance that records in the claim." value of providing roughly that general in view of test character, all numerical value can be thought " approximately " or ".

Though described the various aspects of the compsn of this paper, other particular of the present invention comprises those that provide in the following alphabetic flag paragraph:

AA. the preparation method of cross-linked polymer blend comprises:

A) in first reactor drum, make the polymers soln polymerization that comprises first polymkeric substance;

B) in second reactor drum, make the polymers soln polymerization that comprises second polymkeric substance;

C) said first polymers soln is combined with said second polymers soln to produce blend polymer solution;

D) the said blend polymer solution of processing is to produce blend polymer; With

E) through letting said blend polymer experience high-energy photon make said blend polymer crosslinked at least in part;

The unit of the about 99wt% propylene derived of each self-contained about 75-of wherein said first polymkeric substance and said second polymkeric substance, the approximately unit of the about 25wt% ethylene derivative of 1-and the about about 6wt% diene of 0.05-deutero-unit.

AB. the section AA method, wherein said first polymkeric substance comprises the unit of the about 20wt% ethylene derivative of about 12-.

AC. arbitrary section method in the above-mentioned alphabetic flag paragraph, wherein said first polymkeric substance comprises the unit of the about 18wt% ethylene derivative of about 14-.

AD. arbitrary section method in the above-mentioned alphabetic flag paragraph, wherein said second polymkeric substance comprises the unit of the about 10wt% ethylene derivative of about 3-.

AE. arbitrary section method in the above-mentioned alphabetic flag paragraph, wherein said second polymkeric substance comprises the unit of the about 8wt% ethylene derivative of about 5-.

AF. arbitrary section method in the above-mentioned alphabetic flag paragraph, wherein said first polymkeric substance comprise the about 5wt% diene of about 0.5-deutero-unit.

AG. arbitrary section method in the above-mentioned alphabetic flag paragraph, wherein said first polymkeric substance comprise the about 3wt% diene of about 1-deutero-unit.

AH. arbitrary section method in the above-mentioned alphabetic flag paragraph, wherein said second polymkeric substance comprise the about 1.0wt% diene of about 0.1-deutero-unit.

AI. arbitrary section method in the above-mentioned alphabetic flag paragraph; The unit that wherein said first polymkeric substance comprises the about 18wt% ethylene derivative of about 14-and the approximately about 3wt% diene of 1-deutero-unit and wherein said second polymkeric substance comprise the unit of the about 8wt% ethylene derivative of about 5-and the about about 1.0wt% diene of 0.1-deutero-unit.

AJ. arbitrary section method in the above-mentioned alphabetic flag paragraph, wherein said blend polymer comprises the unit of the about 18wt% ethylene derivative of about 10-.

AK. arbitrary section method in the above-mentioned alphabetic flag paragraph, wherein said blend polymer comprises the unit of the about 16wt% ethylene derivative of about 12-.

AL. arbitrary section method in the above-mentioned alphabetic flag paragraph, wherein said blend polymer comprise the about 5.0wt% diene of about 0.1-deutero-unit.

AM. arbitrary section method in the above-mentioned alphabetic flag paragraph, wherein said blend polymer comprise the about 3.0wt% diene of about 0.5-deutero-unit.

AN. arbitrary section method in the above-mentioned alphabetic flag paragraph, wherein said blend polymer comprise the about 2.0wt% diene of about 1.0-deutero-unit.

AO. arbitrary section method in the above-mentioned alphabetic flag paragraph, wherein said high-energy photon is ultraviolet ray, electronics, x-ray or gamma-radiation form.

AP. arbitrary section method in the above-mentioned alphabetic flag paragraph wherein lets said blend polymer experience the electron beam irradiation of the amount of the about 100kGy of about 30-.

AQ. arbitrary section method in the above-mentioned alphabetic flag paragraph wherein lets said blend polymer experience the electron beam irradiation of the amount of the about 60kGy of about 50-.

AR. arbitrary section method in the above-mentioned alphabetic flag paragraph wherein was configured as one or more fibers, film, non-woven fabric or other goods with said blend polymer before crosslinked.

AS. arbitrary section method in the above-mentioned alphabetic flag paragraph, wherein with said blend polymer before crosslinked with one or more auxiliary agents, inhibitor, elastomer-assisted, Vestolen PP 7052, additive or their any combination compounding.

AT. the method for paragraph AS, wherein said auxiliary agent is a triacrylate.

AU. arbitrary section method among the paragraph AS to AT, wherein said inhibitor is a SULPHOSUCCINIC ACID ESTER.

AV. arbitrary section method among the paragraph AS to AU is wherein with said blend polymer and at least a auxiliary agent and at least a inhibitor compounding.

AW. arbitrary section method among the paragraph AS to AV, wherein said auxiliary agent is that triacrylate and said inhibitor are SULPHOSUCCINIC ACID ESTERs.

AX. arbitrary section method among the paragraph AS to AW wherein further was configured as one or more fibers, film, non-woven fabric or other goods with said compounding blend polymer before the experience high-energy photon.

AY. polymer compsn; Comprise the blend polymer that forms through the reactor blend that produces and be processed in first polymkeric substance that forms in first reactor drum and second polymkeric substance that in second reactor drum, forms; The unit of the about 99wt% propylene derived of each self-contained about 75-of wherein said first polymkeric substance and said second polymkeric substance, the approximately unit of the about 25wt% ethylene derivative of 1-and the about about 6wt% diene of 0.05-deutero-unit.

AZ. the polymer compsn of paragraph AY, wherein said first polymkeric substance comprises the unit of the about 20wt% ethylene derivative of about 12-.

BA. arbitrary section polymer compsn among the paragraph AY to AZ, wherein said first polymkeric substance comprises the unit of the about 18wt% ethylene derivative of about 14-.

BB. arbitrary section polymer compsn among the paragraph AY to BA, wherein said second polymkeric substance comprises the unit of the about 10wt% ethylene derivative of about 3-.

BC. arbitrary section polymer compsn among the paragraph AY to BB, wherein said second polymkeric substance comprises the unit of the about 8wt% ethylene derivative of about 5-.

BD. arbitrary section polymer compsn among the paragraph AY to BC, wherein said first polymkeric substance comprises the about 5wt% diene of about 0.5-deutero-unit.

BE. arbitrary section polymer compsn among the paragraph AY to BD, wherein said first polymkeric substance comprises the about 3.0wt% diene of about 1.0-deutero-unit.

BF. arbitrary section polymer compsn among the paragraph AY to BE, wherein said second polymkeric substance comprises the about 1.0wt% diene of about 0.1-deutero-unit.

BG. arbitrary section polymer compsn among the paragraph AY to BF; The unit that wherein said first polymkeric substance comprises the about 18wt% ethylene derivative of about 14-and the approximately about 3wt% diene of 1-deutero-unit and wherein said second polymkeric substance comprise the unit of the about 8wt% ethylene derivative of about 5-and the about about 1.0wt% diene of 0.1-deutero-unit.

BH. arbitrary section polymer compsn among the paragraph AY to BG, wherein said blend polymer comprises the unit of the about 18wt% ethylene derivative of about 10-.

BI. arbitrary section polymer compsn among the paragraph AY to BH, wherein said blend polymer comprises the unit of the about 16wt% ethylene derivative of about 12-.

BJ. arbitrary section polymer compsn among the paragraph AY to BI, wherein said blend polymer comprises the about 5.0wt% diene of about 0.1-deutero-unit.

BK. arbitrary section polymer compsn among the paragraph AY to BJ, wherein said blend polymer comprises the about 3.0wt% diene of about 0.5-deutero-unit.

BL. arbitrary section polymer compsn among the paragraph AY to BK, wherein said blend polymer comprises the about 2.0wt% diene of about 1.0-deutero-unit.

BM. arbitrary section polymer compsn among the paragraph AY to BL wherein makes it crosslinked at least in part through letting said blend polymer experience high-energy photon.

BN. the polymer compsn of paragraph BM, wherein said high-energy photon is ultraviolet ray, electronics, x-ray or gamma-radiation form.

BO. arbitrary section polymer compsn among the paragraph BM to BN wherein lets said blend polymer experience the electron beam irradiation of the amount of the about 100kGy of about 30-.

BP. arbitrary section polymer compsn among the paragraph BM to BO wherein lets said blend polymer experience the electron beam irradiation of the amount of the about 60kGy of about 50-.

BQ. arbitrary section polymer compsn among the paragraph BM to BP wherein was configured as one or more fibers, film, non-woven fabric or other goods with said blend polymer before crosslinked.

BR. the polymer compsn of paragraph BQ wherein makes said fiber, film, non-woven fabric or other goods crosslinked at least in part via electron beam irradiation.

BS. arbitrary section polymer compsn among the paragraph AY to BR, wherein with said blend polymer further with one or more auxiliary agents, inhibitor, elastomer-assisted, Vestolen PP 7052, additive or their any combination compounding.

BT. the method for paragraph BS, wherein said auxiliary agent is a triacrylate.

BU. arbitrary section method among the paragraph BS to BT, wherein said inhibitor is a SULPHOSUCCINIC ACID ESTER.

BV. arbitrary section method among the paragraph BS to BU is wherein with said blend polymer and at least a auxiliary agent and at least a inhibitor compounding.

BW. arbitrary section method among the paragraph BS to BV, wherein said auxiliary agent is that triacrylate and said inhibitor are SULPHOSUCCINIC ACID ESTERs.

BX. through making among the paragraph AY to BW arbitrary section polymer compsn experience electron beam irradiation make its crosslinked formed partial cross-linked at least polymer compsn.

BY. arbitrary section polymer compsn among the paragraph AY to BX, wherein said blend polymer has the melt flow rate(MFR) of the about 10.0g/10min of about 0.1-.

BZ. arbitrary section polymer compsn among the paragraph AY to BY, wherein said blend polymer has the melt flow rate(MFR) of the about 7.0g/10min of about 3.0-.

CA. arbitrary section polymer compsn among the paragraph AY to BZ, wherein said blend polymer has the MWD of about 1.5-about 10.0.

CB. arbitrary section polymer compsn among the paragraph AY to CA, wherein said blend polymer has the MWD of about 2.0-about 4.0.

CC. arbitrary section polymer compsn among the paragraph AY to CB, wherein said blend polymer has greater than about 110 ℃ melt temperature.

CD. arbitrary section polymer compsn among the paragraph AY to CC, wherein said blend polymer has greater than about 115 ℃ melt temperature.

CE. arbitrary section polymer compsn among the paragraph AY to CD, wherein said blend polymer have than have same composition and exceed about at least 5 ℃ melt temperature through the physical blending of said polymkeric substance rather than the blend polymer that forms through reactor blending.

CF. but the peak stress that arbitrary section crosslinking polymer composition among the paragraph BX to CE, wherein said polymer compsn comprise auxiliary agent and wherein said polymer compsn is greater than with the quadrat method preparation and have same composition do not have the polymkeric substance of auxiliary agent.

CG. but the peak value elongation that arbitrary section crosslinking polymer composition among the paragraph BX to CF, wherein said polymer compsn comprise auxiliary agent and wherein said polymer compsn is greater than with the quadrat method preparation and have same composition do not have the polymkeric substance of auxiliary agent.

CH. but arbitrary section crosslinking polymer composition among the paragraph BX to CG, wherein said polymer compsn comprise and show aspect auxiliary agent and the wherein said polymer compsn tensile deformation after crosslinked than with the quadrat method preparation and have same composition do not have the bigger improvement of polymkeric substance of auxiliary agent.

CI. but the peak stress that arbitrary section crosslinking polymer composition among the paragraph BX to CH, wherein said polymer compsn comprise inhibitor and wherein said polymer compsn is greater than with the quadrat method preparation and have same composition do not have the polymkeric substance of inhibitor.

CJ. but the peak value elongation that arbitrary section crosslinking polymer composition among the paragraph BX to CI, wherein said polymer compsn comprise inhibitor and wherein said polymer compsn is greater than with the quadrat method preparation and have same composition do not have the polymkeric substance of inhibitor.

CK. but arbitrary section crosslinking polymer composition among the paragraph BX to CJ, wherein said polymer compsn comprise and show aspect inhibitor and the wherein said polymer compsn tensile deformation after crosslinked than with the quadrat method preparation and have same composition do not have the bigger improvement of polymkeric substance of inhibitor.

CL. but arbitrary section crosslinking polymer composition among the paragraph BX to CK, wherein said polymer compsn comprise at least one Xiang Yutong quadrat method preparation in peak stress, peak value elongation or the tensile deformation of auxiliary agent and inhibitor and wherein said compsn and have same composition do not have the polymer phase ratio of auxiliary agent and inhibitor to be improved.

CM. partial cross-linked at least polymer compsn comprises the blend polymer that forms through the reactor blend that produces and be processed in first polymkeric substance that forms in first reactor drum and second polymkeric substance that in second reactor drum, forms, wherein:

A) said first polymkeric substance comprises the unit and the about about 3.0wt% diene of 1.0-deutero-unit of the about 18wt% ethylene derivative of about 14-;

B) said second polymkeric substance comprises the unit and the about about 1.0wt% diene of 0.1-deutero-unit of the about 8wt% ethylene derivative of about 5-;

C) with said blend polymer and at least a auxiliary agent and at least a inhibitor compounding; With

D) make it crosslinked at least in part through the polymer compsn experience electron beam irradiation that makes said compounding;

At least one greater than with the quadrat method preparation and have same composition but do not have the polymkeric substance of auxiliary agent and inhibitor in the peak stress of wherein said compsn, peak value elongation or the tensile deformation.

Used one group of numerical upper limits and one group of numerical lower limits to describe some embodiment and characteristic.Self-evident is that the scope from any lower limit to any upper limit should be considered, except as otherwise noted.Some lower limit, the upper limit and scope appear in following one or more claim.All numerical value are " approximately " or " roughly " indicator value, and consider that those skilled in the art are with experimental error and the deviation estimated.

If the term that uses in the claim limits in the above, then should give the wideest definition for it, because having known this term, the association area personnel are reflected in the patent of publication or announcement of at least one piece of printing.In addition, all patents of quoting among the application, testing sequence and other document are consistent with the present invention and for reference to fully introducing on the degree of all authorities that allow this introducing in this publication.

Though foregoing relates to embodiment of the present invention, can under the situation that does not break away from base region of the present invention, design of the present invention other with other embodiment, and scope of the present invention is confirmed by subsequently claim.

In the accompanying claims each limits independently invention, and it should be believed to comprise the various elements stipulated in these claims or the equivalent of restriction in order to prevent to encroach right.Depend on context, all references to " the present invention " can only be meant the embodiment that some is concrete in some cases here.In other cases, should approve and to be meant the theme of quoting among one or more (but not necessarily whole) in the claim quoting of " the present invention ".Among the present invention each has been described here; Comprise concrete embodiment, pattern and embodiment; But the invention is not restricted to these embodiments, pattern or embodiment, they are included into is in order to make those skilled in the art when the information in this patent is combined with technology with obtainable information, can make and use the present invention.

Claims

1. the preparation method of cross-linked polymer blend comprises:

2. the process of claim 1 wherein that said first polymkeric substance comprises the unit of the about 20wt% ethylene derivative of about 12-.

3. the process of claim 1 wherein that said first polymkeric substance comprises the unit of the about 18wt% ethylene derivative of about 14-.

4. the process of claim 1 wherein that said second polymkeric substance comprises the unit of the about 10wt% ethylene derivative of about 3-.

5. the process of claim 1 wherein that said second polymkeric substance comprises the unit of the about 8wt% ethylene derivative of about 5-.

6. the process of claim 1 wherein that said first polymkeric substance comprises the about 5wt% diene of about 0.5-deutero-unit.

7. the process of claim 1 wherein that said first polymkeric substance comprises the about 3wt% diene of about 1-deutero-unit.

8. the process of claim 1 wherein that said second polymkeric substance comprises the about 1.0wt% diene of about 0.1-deutero-unit.

9. the method for claim 1; The unit that wherein said first polymkeric substance comprises the about 18wt% ethylene derivative of about 14-and the approximately about 3wt% diene of 1-deutero-unit and wherein said second polymkeric substance comprise the unit of the about 8wt% ethylene derivative of about 5-and the about about 1.0wt% diene of 0.1-deutero-unit.

10. the process of claim 1 wherein that said blend polymer comprises the unit of the about 18wt% ethylene derivative of about 10-.

11. the process of claim 1 wherein that said blend polymer comprises the unit of the about 16wt% ethylene derivative of about 12-.

12. the process of claim 1 wherein that said blend polymer comprises the about 5.0wt% diene of about 0.1-deutero-unit.

13. the process of claim 1 wherein that said high-energy photon is ultraviolet ray, electronics, x-ray or gamma-radiation form.

14. the process of claim 1 wherein and let said blend polymer experience the electron beam irradiation of the amount of the about 100kGy of about 30-.

15. the process of claim 1 wherein said blend polymer was configured as one or more fibers, film, non-woven fabric or other goods before crosslinked.

16. the process of claim 1 wherein that said auxiliary agent is a triacrylate.

17. the process of claim 1 wherein that said inhibitor is a SULPHOSUCCINIC ACID ESTER.

18. the process of claim 1 wherein the blend polymer of said compounding further was configured as one or more fibers, film, non-woven fabric or other goods before the experience high-energy photon.

19. polymer compsn; Comprise the blend polymer that forms through the reactor blend that produces and be processed in first polymkeric substance that forms in first reactor drum and second polymkeric substance that in second reactor drum, forms; The unit of the about 99wt% propylene derived of each self-contained about 75-of wherein said first polymkeric substance and said second polymkeric substance, the approximately unit of the about 25wt% ethylene derivative of 1-and the about about 6wt% diene of 0.05-deutero-unit.

20. the polymer compsn of claim 19; The unit that wherein said first polymkeric substance comprises the about 18wt% ethylene derivative of about 14-and the approximately about 3wt% diene of 1-deutero-unit and wherein said second polymkeric substance comprise the unit of the about 8wt% ethylene derivative of about 5-and the about about 1.0wt% diene of 0.1-deutero-unit.

21. the polymer compsn of claim 19, wherein said high-energy photon are ultraviolet ray, electronics, x-ray or gamma-radiation form.

22. the polymer compsn of claim 19 wherein lets said blend polymer experience the electron beam irradiation of the amount of the about 100kGy of about 30-.

23. the polymer compsn of claim 19 wherein makes said fiber, film, non-woven fabric or other goods crosslinked at least in part via electron beam irradiation.

24. the polymer compsn experience electron beam irradiation through making claim 19 makes its crosslinked formed partial cross-linked at least polymer compsn.

25. partial cross-linked at least polymer compsn comprises the blend polymer that forms through the reactor blend that produces and be processed in first polymkeric substance that forms in first reactor drum and second polymkeric substance that in second reactor drum, forms, wherein:

D) make it crosslinked at least in part through the polymer compsn experience electron beam irradiation that makes compounding;

At least one greater than with the quadrat method preparation and have same composition but do not have the analog value of the polymkeric substance of auxiliary agent and inhibitor in the peak stress of wherein said polymer compsn, peak value elongation or the tensile deformation.